EP0917548B1 - Procede de fabrication de polyorganosiloxanes (pos) multifonctionnels, par deshydrogenocondensation et hydrosilylation - Google Patents

Procede de fabrication de polyorganosiloxanes (pos) multifonctionnels, par deshydrogenocondensation et hydrosilylation Download PDF

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Publication number
EP0917548B1
EP0917548B1 EP97936745A EP97936745A EP0917548B1 EP 0917548 B1 EP0917548 B1 EP 0917548B1 EP 97936745 A EP97936745 A EP 97936745A EP 97936745 A EP97936745 A EP 97936745A EP 0917548 B1 EP0917548 B1 EP 0917548B1
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EP
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Prior art keywords
pos
reactor
hydrogen
hxr
group
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Expired - Lifetime
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EP97936745A
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German (de)
English (en)
French (fr)
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EP0917548A1 (fr
Inventor
Christian Priou
Robert Violland
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the field of the invention is that of the functionalization of silicones, in particular polyorganosiloxanes, linear or cyclic, consisting of units M, D, T and, optionally, Q.
  • POSs to be functionalized are polyorganohydrogensiloxanes, linear or cyclical. It is the SiH groupings of these POSs which serve as points of attachment, to the functionalities intended to replace these POS, for their confer specific properties, for example, anti-adhesion, lubrication or compatibilization ..., so many properties sought in diverse and varied applications of silicones.
  • the present invention relates to the manufacture, on an industrial scale, of these multifunctional POS.
  • the modes of continuous or semi-continuous operation are better suited to requirements industrial profitability and productivity, as discontinuous mode.
  • Dehydrogenocondensation is carried out by bringing the POS (I) to SiH, with an alcohol precursor of the alkoxy functionality, in the presence of a platinum-based catalyst.
  • the POS (II) thus obtained is then subjected to hydrosilylation of a olefin, such as octene, by the remaining SiHs and in the presence of the catalyst starting plate.
  • a olefin such as octene
  • the general specifications of an industrial process for manufacturing Multifunctional POS includes at least four major requirements: productivity and profitability, quality of finished products, safety and simplicity of implementation.
  • One of the determining factors of the quality of POS multifunctionalized considered is based on the control of the transformation rate SiH by dehydrogenocondensation (substitution rate with a first type functionality). If alcohol is used as the reagent dehydrogenocondensation, it is important to control the degree of alkoxylation partial, so as to ensure its reproducibility.
  • the only prior art close to this regard namely PCT application WO 96/16125, does not provide any solution (nor even at the beginning of the solution), because the examples she gives are tests of laboratory carried out, discontinuously, in 500 ml three-necked flasks.
  • the industrial security aspect is also very restrictive in this multifunctionalization process, for several reasons.
  • the first is that the release of hydrogen specific to dehydrogenocondensation is a an obvious threat that should be brought under control.
  • one of the essential objectives of the present invention is to improve the method of multifunctionalization of POS described in WO 96/16125 to make it an industrial method of manufacturing multifunctional POS by dehydrogenocondensation / hydrosilylation, respecting requirements of profitability and productivity, quality of finished product, safety and, finally, simplicity of implementation, said process calling for its implementation an industrial manufacturing device having to be economical, reliable , efficient and adapted to the aforementioned manufacturing process.
  • the process according to the invention allows, incidentally, to evacuate conveniently the heat of reaction, while controlling the temperature of the reaction mass.
  • Another advantage of the invention is the economics of this process.
  • the device shown comprises a continuous reactor A dehydrogenocondensation and a batch B hydrosilylation reactor.
  • the device shown can comprise several reactors B operating, either semi-continuously (alternating reaction / drain sequences), or continuously, or even a single reactor B designed to operate continuously.
  • the reactor A is essentially constituted by an enclosure 1 , in the general form of a hollow cylindrical column. This column is subdivided, on the one hand, into at least one - in this case a - reaction lower chamber 2 and, on the other hand, into an upper chamber 3 belonging to the means of evacuation and rapid recovery of the gas and containing any means of hydrogen separation.
  • the lower chamber 2 is provided with at least one - in this case a - tray 40 constituting the bottom of a main compartment 5, intended to serve as a seat for at least part of the dehydrogenocondensation of the POS (I).
  • the lower chamber 2 is of the multi-stage type and comprises at least one other lower stage - preferably one to three and, in this case three - in addition to that corresponding to the compartment main 5.
  • Each lower stage comprises a bottom, formed by at least one - in this case a - plate 41, 42, 43, defining, with the bottom of the upper vicinal stage, a compartment 6, 7 and 8 respectively, for the plates 41, 42 , 43.
  • Each plate 40, 41, 42, 43 comprises at least one overflow member ( 13 , 13 ' ) (in this case a) allowing the adjustment of the level of liqu reaction idea.
  • the reference 13 designates the overflow of the plate 40 (main compartment 5 ).
  • the references 13 ' designate the overflows of the plates 41, 42, 43 (lower compartments 6, 7 and 8).
  • the main compartment 5 is the one into which opens the supply line (s) 11 and 12 for reagents.
  • the overflow member 13, equipping this main compartment 5 determines a given level for the liquid reaction medium in the compartment 5.
  • This overflow 13 places the compartment 5 in communication with the lower level of the lower chamber 2, where the transfer pipe is located 10.
  • this lower level of the lower chamber 2 corresponds to the base 9, which is separated from the main compartment 5 by three lower compartments 6, 7, 8.
  • the compartment main 5 is in relation, through its upper part, to the upper chamber 3.
  • the main compartment 5 can be supplied with liquid reaction medium continuously via the supply conduits 11 and 12.
  • the latter make it possible to convey continuously, for example, the POS (I) and the reagent HXR (eg alcohol).
  • the reactor A is preferably supplied substantially with POS (I) at SiH and with functional reagent HXR, the catalyst being included in the POS ( I) and / or the HXR reagent.
  • the use of a catalyst solution in the HXR reagent is preferred.
  • a hydrogen reagent mobile - such as alcohol (ethanol) - improves safety because it can control and temper the jolts of reaction and release associated hydrogen.
  • preheating of at least one of the starting reagents namely: POS (I), HXR and catalyst, at a temperature between 30 and 100 ° C, preferably between 40 and 80 ° C.
  • This overflow tube 13 is axial relative to the enclosure 1 of the reactor A and, preferably, extends upwards, to put the compartment 5 in communication with the upper chamber 3. To do this , the tube 13 extends through a partition 15 of separation. The upper part of the tube 13, emerging in the upper chamber 3 above the partition 15, is provided with an opening 16. This tube 13 allows the rapid evacuation, in the upper chamber 3, of the gas formed in the compartment main 5.
  • This tube 13 can optionally be equipped with at least one non-return valve in place of the orifice 16. According to the invention, one or more tubes 13 can be provided for conveying the gases from compartment 5 to the upper room 3.
  • the other overflow members 13 ' equipping the plates 41, 42 and 43, also consist of cylindrical tubes whose axes are not aligned with each other.
  • each lower compartment 6, 7, 8, as well as the base 9, is intended to be supplied with a liquid reaction medium via the overflow 13, 13 ' of the immediately upper stage.
  • the bottom of the lowest stage 8 communicates, by its overflow 13 ', with the base 9 of the reactor A, so as to allow the collection of the POS (II).
  • the residence time of the liquid reaction medium in each compartment can be adjusted as desired, by varying the withdrawal levels of the various plates 40, 41, 42, 43.
  • Drain pipes 17 are connected to the lower part of each compartment 5, 6, 7, 8. These pipes 17 include valves symbolically shown in the drawing but not referenced.
  • the upper chamber 3 As regards the upper chamber 3, it is delimited vertically by the partition 15 of separation with the lower chamber 2 and by the top of the column 1 of the reactor A. It should be noted that it belongs to the means for rapid evacuation and recovery of the gas emerging from the lower chamber 2 during operation. This gas then passes successively through the orifice 14, the lumen and the opening 16 of the tube 13.
  • this upper chamber 3 comprises means 18 for separating the hydrogen from the other components of the gas produced during the dehydrogenocondensation.
  • the means 18 are therefore advantageously constituted by at least one condenser - in this case one - symbolized by a coil in the upper chamber 3 and supplied with refrigerant according to a flow indicated by the arrows f shown in the drawing.
  • the latter also shows, schematically, a pipe 19 for evacuating the hydrogen separated from the volatile vapors.
  • This pipe 19 is connected to the upper part of column 1.
  • the device for implementing the method according to the invention comprises means for continuously determining the rate of substitution of SiH, so as to allow regulation thereof.
  • These means are preferably essentially constituted by at least one hydrogen meter, advantageously associated with a calculation unit.
  • Such means can be provided on (or put in relation to) the pipe 19 and they can be connected to a continuous control and regulation system of the substitution rate, also called transformation rate .
  • This control system could, for example, ensure regulation by acting on the feed rates and / or on the residence times in the different stages by modifying the overflow heights of each overflow 13, 13 ′.
  • This residence time depends directly on the moment of transfer of the POS (II) in the reactor B.
  • the degree of substitution of SiH by Fo 1 is measured and / or calculated and the transfer of the POS (II) from the dehydrogeno-condensation reactor A to the hydrosilylation reactor B, as soon as the rate of substitution of SiH by Fo 1 , expressed in molar%, is greater than or equal to 45, preferably 55 and , more preferably still, is between 60 and 70. This is one of the means available, among others, to regulate the substitution rate.
  • monitoring the substitution rate or transformation rate can, advantageously, be done by measuring the hydrogen released.
  • the flow thus measured allows access, by calculation, directly to the substitution rate.
  • a alternative would be to set up a continuous analysis of the POS (II).
  • instant knowledge of the rate of substitution allows to regulate it by playing on the operating parameters, in particular on the residence time of the POS (I) and (II) in the reactor A and / or on the reaction temperature and / or on the supply flows in POS (I), in reagent functional HXR and catalyst.
  • the condensate produced by the condenser 18 is collected in the bottom of the lower chamber 3, constituted by the partition 15.
  • the draw-off line 20 would then be connected to the main compartment 5 , so as to allow the latter to be supplied with recovered HXR.
  • This variant corresponds to a preferred method of the method and of the device according to the invention.
  • the bottom (or the partition) 15 is eliminated. Under these conditions, the HXR condensate recovered is directly collected in the main compartment 5 on the tray 40 .
  • reaction temperature is regulated by example at around 70-71 ° C. This regulation is another important factor for stabilization of the transformation rate of POS (I) into POS (II), at the value almost asymptotic by about 66%.
  • Such a multi-stage continuous A reactor makes it possible to have large exchange surfaces, which facilitate the dehydrogenocondensation and the evacuation of the gas formed containing the hydrogen and the vapors of volatiles. By multiplying the stages, this exchange surface is increased by the same amount which can also be increased by varying the diameter of the column and the separation plates 40 to 43 .
  • Such a reactor A also makes it possible to optimize the free starting surface of the hydrogen, which makes it possible to avoid unacceptable foaming. It also offers the possibility of controlling, with precision, the rate of substitution of the SiHs of POS (I) by the functionalities Fo 1 , by providing for a control as presented above.
  • this reactor A is compact, of simple structure and inexpensive, is also a significant advantage.
  • this reactor allows the transfer of POS (II) into reactor B, for the purpose of neutralization by hydrosilylation, as soon as the rate of asymptotic transformation or substitution into Fo 1 is reached. .
  • the reactor B is a discontinuous hydrosilylation reactor, designated by the reference 21. It is a tank comprising stirring means 22, formed eg by a propeller stirrer. The bottom of this reactor 21 is connected to a pipe 23 allowing the recovery of the POS (III) once formed.
  • this reactor 21 includes means 24 for recovering the gaseous vents, constituted by a column communicating with the interior of the reactor 21 and preferably comprising an equipment 25 for treating the vents to separate the hydrogen from the other gas.
  • the latter consist of the vapors of volatile reactants, which can be the compound with mobile hydrogen (eg alcohol) and the unsaturated compound to be hydrosilylated (eg alkene).
  • this equipment 25 is constituted by at least one - in this case a - condenser of volatile vapors.
  • This condenser is, for example, a coil (symbolically represented in the figure) traversed by a flow of refrigerant, also indicated in the drawing.
  • the condensates may be recovered in the bottom 25 of the condenser to be stored and / or recycled.
  • R represents a hydrocarbon residue consisting of an alkyl radical, linear or branched, having from 1 to 15 atoms of carbon and, preferably, having from 1 to 6 carbon atoms.
  • the functionality Fo 1 is an alkoxyl and in the case where the unsaturated compound to be hydrosilylated is an olefin, Fo 2 is a functional hydrocarbon radical corresponding to the same definition as that given for W in formula (II) of the motif constituting the functionalized POSs, as described in WO 96/16125.
  • the functionalities Fo 1 are for example methoxyl, ethoxyl and (iso) propoxyl.
  • the functionalities Fo 2 are for example: an alkyl radical (i ') consisting of octyl, dodecyl, undecyl and tridecyl; an alkenyl radical (2i ') consisting of hexenyl and dodecenyl; an unsaturated cycloaliphatic radical (3i ') consisting of cyclohexenyl, methyl-1 cyclohexene-1 yl, optionally linked to silicon by the residue -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) - or - (CH 2 ) 3 -.
  • C 1 -C 15 preferably C 1 -C 6, alcohols are preferred. This does not preclude the implementation of their thiol correspondents.
  • unsaturated compound precursor of Fo 2 it is selected from the compounds of appropriate structure capable of leading, by hydrosilylation, to the functionalities corresponding to the groups (i) to (7i) defined above.
  • the precursor unsaturated compounds are selected from olefins capable of leading to the functionalities Fo 2 chosen from the groups (i), (2i) and (3i) defined above.
  • the catalyst is based on platinum. It can be, by example, of platinum with an oxidation state of 0, such as the Karstedt catalyst, but also of platinum at oxidation degrees II or IV. Another alternative is to use platinum catalysts supported on mineral charges, such as e. g. carbon black, silica, alumina.
  • the POS (I), on the one hand, and the ethanol + the platinum catalyst, on the other hand, are introduced into the compartment 5 by the pipes 11 and 12 respectively.
  • the feed rates are specified above.
  • the dehydrogenocondensation reaction takes place in the main compartment 5 with the release of hydrogen and volatiles which pass into the upper chamber 3 via the tube 13.
  • the volatiles are condensed by the condenser 18 and recovered by the line 20, then recycled by transporting them to the main compartment 5.
  • the hydrogen, separated from the condensable volatiles escapes via the line 19 and is recovered.
  • the liquid reaction medium After a certain supply time, the liquid reaction medium reaches its overflow level in compartment 5. This level corresponds to a certain residence time, equal in this case to 3 min 30 s and pours into the compartment lower 6.
  • the liquid overflow volume of compartment 5 is 470 ml, while, for the other three compartments (stages) 6, 7, 8, this volume is 630 ml.
  • the system for cascading the liquid reaction medium continues in the lower compartments 7 and 8 and, in fine, in the pellet 9, the POS (II) is collected, the conversion rate of which is 0.66.
  • This rate is regulated by a servo system comprising a hydrogen sensor and a calculation unit continuously determining the transformation rate, which allows it to be regulated by varying the flow rates during operation. We could also adjust the overhangs of the trays 40 to 43.
  • the POS (II) thus obtained is continuously transferred via line 10 into reactor B, to be subjected to hydrosilylation making it harmless and transforming it into POS (III).
  • the volatilized ethanol and octene are condensed then recovered and possibly recycled using means 24.
  • the POS (III) is recovered by draining the reactor 21 using the line 23.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
EP97936745A 1996-08-06 1997-08-06 Procede de fabrication de polyorganosiloxanes (pos) multifonctionnels, par deshydrogenocondensation et hydrosilylation Expired - Lifetime EP0917548B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9610086 1996-08-06
FR9610086A FR2752239B1 (fr) 1996-08-06 1996-08-06 Procede de fabrication de polyorganosiloxanes (pos) multifonctionnels, par deshydrogenocondensation et hydrosilylation, et dispositif pour la mise en oeuvre de ce procede
PCT/FR1997/001458 WO1998005700A1 (fr) 1996-08-06 1997-08-06 Procede de fabrication de polyorganosiloxanes (pos) multifonctionnels, par deshydrogenocondensation et hydrosilylation, et dispositif pour la mise en oeuvre de ce procede

Publications (2)

Publication Number Publication Date
EP0917548A1 EP0917548A1 (fr) 1999-05-26
EP0917548B1 true EP0917548B1 (fr) 2002-06-12

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EP97936745A Expired - Lifetime EP0917548B1 (fr) 1996-08-06 1997-08-06 Procede de fabrication de polyorganosiloxanes (pos) multifonctionnels, par deshydrogenocondensation et hydrosilylation

Country Status (13)

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EP (1) EP0917548B1 (pt)
JP (1) JP3197281B2 (pt)
AR (1) AR008825A1 (pt)
AT (1) ATE219118T1 (pt)
AU (1) AU3945597A (pt)
BR (1) BR9711029A (pt)
DE (1) DE69713340T2 (pt)
DK (1) DK0917548T3 (pt)
ES (1) ES2174277T3 (pt)
FR (1) FR2752239B1 (pt)
PT (1) PT917548E (pt)
WO (1) WO1998005700A1 (pt)
ZA (1) ZA976468B (pt)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5986022A (en) * 1998-04-01 1999-11-16 Witco Corporation Continuous manufacture of silicone coploymers
DE19816921A1 (de) * 1998-04-16 1999-10-21 Wacker Chemie Gmbh Verfahren für kontinuierliche polymeranaloge Umsetzungen
DE19859759C1 (de) * 1998-12-23 2000-06-29 Goldschmidt Ag Th Verfahren und Vorrichtung zur Durchführung kontinuierlicher Hydrosilylierungsreaktionen
FR2806930B1 (fr) * 2000-04-04 2002-06-28 Rhodia Chimie Sa Utilisation d'un derive de bore a titre de catalyseur thermoactivable pour la polymerisation et/ou reticulation de silicone par deshydrogenocondensation
KR102309818B1 (ko) * 2019-12-02 2021-10-12 한국도로공사 팽창줄눈 구조체 및 이를 이용한 콘크리트 포장 방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5750643A (en) * 1993-05-18 1998-05-12 Sri International Dehydrocoupling treatment and hydrosilylation of silicon-containing polymers, and compounds and articles produced thereby
FR2707655B1 (fr) * 1993-07-02 1995-09-15 Rhone Poulenc Chimie Nouveaux polymères siliconés à fonctions oléfiniques, leur procédé de préparation et compositions durcissables comprenant lesdits polymères.
FR2727118B1 (fr) * 1994-11-18 1997-01-03 Rhone Poulenc Chimie Polyorganosiloxanes fonctionnalises et l'un de leurs procedes de preparation
FR2727119B1 (fr) * 1994-11-18 1997-01-03 Rhone Poulenc Chimie Polyorganosiloxanes fonctionnalises et l'un de leurs procedes de preparation

Also Published As

Publication number Publication date
DE69713340T2 (de) 2003-01-02
PT917548E (pt) 2002-09-30
AR008825A1 (es) 2000-02-23
FR2752239A1 (fr) 1998-02-13
BR9711029A (pt) 1999-08-17
EP0917548A1 (fr) 1999-05-26
WO1998005700A1 (fr) 1998-02-12
FR2752239B1 (fr) 1998-12-04
ATE219118T1 (de) 2002-06-15
ES2174277T3 (es) 2002-11-01
DK0917548T3 (da) 2002-07-15
JP2000502745A (ja) 2000-03-07
DE69713340D1 (de) 2002-07-18
AU3945597A (en) 1998-02-25
JP3197281B2 (ja) 2001-08-13
ZA976468B (en) 1998-02-19

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